High efficiency erosion resistant silicone ablator composition

ABSTRACT

A lightweight ablator formulation has been developed which offers superior thermal performance compared to current state of the art ablator formulations. The lightweight ablator formulations described herein typically include at least one endothermically decomposing (energy absorbing) material with a fluxing agent resulting in significantly reduced backface temperature response and a more stable surface. According to one implementation the ablator composition comprises about 30 to about 70 percent by weight of a base silicone resin, about 25 to about 67 percent by weight of a low-density filler, about 3 to about 7 percent by weight of a curing agent and greater than 0 and up to about 10 percent by weight of a boron-containing compound.

RELATED APPLICATION

This application is a continuation of co-pending U.S. patent applicationSer. No. 16/387,033, filed Apr. 17, 2019, which is a continuation ofU.S. patent application Ser. No. 15/254,787, filed Sep. 1, 2016, nowU.S. Pat. No. 10,308,789, which is a continuation of U.S. patentapplication Ser. No. 14/317,920, filed Jun. 27, 2014, now U.S. Pat. No.9,458,356. The aforementioned related patent applications are hereinincorporated by reference in their entirety.

FIELD

The implementations described herein generally relate to ablatorcompositions and more particularly to low-density yet highly durableablator compositions and methods for mixing the compositions and formingablative thermal protections systems.

BACKGROUND

Ablative materials have been used in a variety of applications toprotect and insulate structures subjected to extreme thermal conditions.For example, many aerospace vehicles that traverse, exit, and enter theatmosphere of the Earth travel at high velocities, and as a result,their exterior aerosurfaces, and to some degree their substructure,experience high aerothermal loads. Aerothermal loads have been managedusing a variety of techniques including insulation, radiant cooling,active cooling, conduction and convective cooling, and by phase changeor ablative materials. Generally, ablative materials are applied to theaffected aerosurfaces to absorb the extreme heat in order to insulatethe vehicle from the thermal environment.

Known ablative materials comprise a variety of constituent components,each at certain percentages by weight or volume, to achieve a balance ofthermal protection and other physical properties. Generally, ablatorcompositions are a composite material comprising a resin matrix with avariety of filler materials to reduce the overall density or provideother physical properties.

Known ablative materials typically have performance envelopes in whichthese known ablative compositions perform effectively. When exposed toheating or pressures in excess of these envelopes these known ablativecompositions can erode rapidly, requiring excessive thickness (weight)of the material. When used in more benign environments, these knownablator compositions function as poor insulators, also requiringadditional thickness.

Accordingly, there remains a need in the art for an ablator compositionthat is of low-density yet has high erosion resistance and durabilitybefore, during, and after high thermal loads, and which is relativelylow cost and simple to fabricate.

SUMMARY

The implementations described herein generally relate to ablatorcompositions and more particularly to low-density yet highly durableablator compositions and methods for mixing the compositions and formingablative thermal protections systems. According to one implementation,an ablator composition for providing ablation protection after curethereof is provided. The ablator composition comprises about 30 to about70 percent by weight of a base silicone resin, about 25 to about 67percent by weight of a low-density filler, about 3 to about 7 percent byweight of a curing agent and greater than 0 and up to about 10 percentby weight of a boron-containing compound.

In another implementation described herein, a method of forming anablative structure is provided. The method comprises (a) forming anablator composition, (b) forming the ablator composition into ageometrical shape, and (c) curing the geometrical shape. The ablatorcomposition is formed by mixing about 30 to about 70 percent by weightof a base silicone resin, about 25 to about 67 percent by weight of alow-density filler, about 3 to about 7 percent by weight of a curingagent and greater than 0 and up to about 10 percent by weight of aboron-containing compound.

In yet another implementation described herein, a method of mixing alow-density ablator composition is provided. The method comprises (a)placing approximately 30 to about 70 percent by weight of a basesilicone resin into a container, (b) mixing approximately 3-7 percent byweight of a curing agent with the base silicone resin, (c) mixinggreater than 0 and up to about 10 percent by weight of aboron-containing compound with the resulting mixture of (b), and (d)mixing approximately 25-67 percent by weight of a low-density fillermaterial with the resulting mixture of (c).

In yet another implementation, a substrate having an ablative coatingformed thereon, wherein the ablative coating is formed by curing theablative composition described below is provided.

BRIEF DESCRIPTION OF ILLUSTRATIONS

So that the manner in which the above-recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure briefly summarized above may be had by reference toimplementations, some of which are illustrated in the appended drawings.It is to be noted, however, that the appended drawings illustrate onlytypical implementations of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective implementations.

FIG. 1 is a perspective view of an aerospace vehicle making use of anablator composition formed in accordance with implementations of thepresent disclosure;

FIG. 2 is a cross-sectional view of an ablator compositions formed on astructure in accordance with implementations of the present disclosure;

FIG. 3 is a top view of a honeycomb core embedded in an ablatorcomposition in accordance with implementations of the presentdisclosure; and

FIG. 4 is a top view of scoring an ablator composition in accordancewith implementations of the present disclosure.

To facilitate understanding, identical reference numerals have beenused, wherever possible, to designate identical elements that are commonto the Figures. Additionally, elements of one implementation may beadvantageously adapted for utilization in other implementationsdescribed herein.

DETAILED DESCRIPTION

The following disclosure describes ablator compositions and moreparticularly low-density yet highly durable ablator compositions andmethods for mixing the compositions and forming ablative thermalprotections systems. Certain details are set forth in the followingdescription and in FIGS. 1-4 to provide a thorough understanding ofvarious implementations of the disclosure. Other details describingwell-known structures and systems often associated with ablatorcompositions and forming ablative thermal protection systems are not setforth in the following disclosure to avoid unnecessarily obscuring thedescription of the various implementations.

Many of the details, dimensions, angles and other features shown in theFigures are merely illustrative of particular implementations.Accordingly, other implementations can have other details, components,dimensions, angles and features without departing from the spirit orscope of the present disclosure. In addition, further implementations ofthe disclosure can be practiced without several of the details describedbelow.

A lightweight ablator formulation has been developed which offerssuperior thermal performance compared to current state of the artablator formulations. The lightweight ablator formulations describedherein typically include at least one endothermically decomposing(energy absorbing) material with a fluxing agent resulting insignificantly reduced backface temperature response and a more stablesurface. In some implementations, the ablative materials formed from theablator formulations described herein take advantage of different heatdissipation mechanisms, improving thermal conductivity performance aswell as reducing the weight of the ablative materials. In someimplementations described herein, the ablator compositions cure at anelevated temperature. In some implementations described herein, theablator compositions cure at room temperature.

Implementations described herein utilize endothermically decomposingmaterials in a silicone matrix to allow for generation of gaseousthermal decomposition products and their venting through the lightweightmatrix without causing excessive matrix swelling or spalling. In someimplementations, the silicone matrix may be porous. In someimplementations, the endothermically decomposing material is aboron-containing compound. Exemplary boron containing compounds includeboric acid and ammonium biborate. Not to be bound by theory but it isbelieved that boric acid provides both an endothermically decomposingmaterial and fluxing agent, which allows the low-density filler material(e.g., silica glass microballoons) to fuse in the decomposition zone(e.g., the region where the virgin materials thermally decompose andbecome char) and create a network of glass reinforcement in the weakdecomposition zone without the limitations of glass fiber reinforcementwhich may increase mastic stiffness making packing into corereinforcements difficult. In implementations where the endothermicallydecomposing material is boric acid, boric acid may provide a higherdecomposition onset temperature than alternate boron sources (e.g.,ammonium biborate) which enables the heat cure of the ablatorcomposition on large vehicles instead of a room-temperature curingformulation that has a more limited work life. In some implementations,the ablator composition described herein enables the utilization of alower thickness heat shield, resulting in lower vehicle weight, lowercost and/or higher payload mass.

In some implementations, the resulting ablator composition describedherein has a low-density, approximately 0.3 to 0.6 g/cc (approximately18.7 to 37.5 lb/ft³). Further, the ablator composition described hereincan withstand temperatures up to approximately 1650 degrees Celsius(3002 degrees Fahrenheit) while ablating slowly.

Referring to FIG. 1 an exemplary aerospace vehicle structure 100 isshown with an ablator composition 110 of the present disclosure appliedto the exterior surfaces of the exemplary spacecraft. The exemplaryaerospace vehicle structure 100 is shown flying through the atmosphereof the Earth, where high velocities create extremely elevated thermalloads across the exterior surface, or aerosurface, of the aerospacevehicle structure 100. Accordingly, the ablator composition providesthermal protection for the vehicle during these extreme thermalconditions. While the ablator composition is shown on a manned aerospacevehicle structure 100, it will be appreciated that the ablatorcomposition and products containing the ablator composition are wellsuited for a variety of other manned and unmanned space vehicles thatare expected to encounter high temperatures on their exterior surfacesduring travel through the Earth's, or a planetary atmosphere. Theablator composition and products containing the ablator composition arepotentially usable on other forms of vehicles, and possibly even onfixed (i.e., non-mobile) structures. The ablator composition may finduse on virtually any form of mobile airborne platform or ground basedvehicle, or possibly even on marine vehicles.

Referring to FIG. 2, the ablator composition 110 is shown applied to aportion of the outer moldline (OML) 200 of the aerospace vehiclestructure 100. In addition to protecting the OML 200, the ablatorcomposition 110 further provides protection to substructure 210 adjacentthe OML 200. Accordingly, additional structure and/or systems withinclose proximity of the OML 200 are protected from the extreme thermalenvironment by the ablator composition 110.

The application of the ablator composition 110 to an aerospace vehicleshould not be construed as limiting; rather the application is merelyillustrative of one structure and one operating environment in which theimplementations of the present disclosure has particular utility. Theablator composition of the present disclosure can further be employedwith a wide variety of structures and systems that must withstand highthermal loads for an extended duration.

In some implementations, the ablator composition 110 of the presentdisclosure generally comprises (1) a base silicone resin; (2) a curingagent; (3) a low-density filler material; (4) at least oneendothermically decomposing material; (5) optionally a thinning fluid;and (6) other additives.

The silicone resin serves as a binder for the low-density fillermaterial and is a secondary contributor to the thermal conductivity ofthe ablator composition 110. The silicone resins, which may be employedin the ablator composition 110, are typically non-elastomeric resinsand, when cured, are highly cross-linked, relatively rigid inflexiblesolids, with the molecular chains linked through oxygen atoms. Suchresins, when used in the ablator composition 110, may be cured, uncuredor partially cured. One exemplary resin is a partially cured lowmolecular weight phenyl methyl polysiloxane resin sold by Dow-Corning ofMidland, Mich., although other silicone resins may also be used. Whenuncured or partially cured silicone resins are used, curing is effectedalong with the silicone resin at room temperature by the curing agentfor the silicone resin.

In some implementations, the base silicone resin comprises from about20% to about 80% by weight of the ablator composition 110. In someimplementations, the base silicone resin comprises from about 30% toabout 70% by weight of the ablator composition 110. In someimplementations, the base silicone resin comprises from about 40% toabout 60% by weight of the ablator composition 110. In someimplementations, the base silicone resin comprises from about 42% toabout 50% by weight of the ablator composition 110.

The curing agent is added to the ablator composition to causecross-linking of the polymer chains in the base silicone resin. Thecuring agents can be many different compounds known to a person skilledin the art.

In some implementations, the curing agent comprises from about 1% toabout 15% by weight of the ablator composition 110. In someimplementations, the curing agent comprises from about 1% to about 10%by weight of the ablator composition 110. In some implementations, thecuring agent comprises from about 2% to about 7% by weight of theablator composition 110. In some implementations, the curing agentcomprises from about 3% to about 5% by weight of the ablator composition110.

In some implementations, the weight ratio of base silicone/curing agentcan be in the range between 8 and 12; in the range between 9.0 and 11.5;or in the range between 9.5 and 11; for example the ratio may be around10. For example, about 10 g of silicone or between 9.8 g and 10.5 g ofsilicone can be mixed with about 1 g of curing agent or between 0.9 and1.2 g of curing agent. The base monomer and the curing agent may be partof two-part silicone elastomer kit. Exemplary silicone elastomer kitsinclude SYLGARD® 182 or SYLGARD® 184 Silicone Elastomer Kit availablefrom the Dow Corning Corporation. SYLGARD® 182 may be used in ablatorformulations where it is desirable to cure the ablator formulation atelevated temperatures. SYLGARD® 184 may be used in ablator formulationswhere it is desirable to cure the ablator formulation at roomtemperature.

The low-density filler material is generally used to reduce overalldensity of the ablator composition 110 and is a primary contributor toreducing thermal conductivity. In some implementations, the bulk densityof the low-density filler material is between approximately 0.1 g/cc and0.50 g/cc. In some implementations, the bulk density of the low-densityfiller material is between approximately 0.15 g/cc and 0.31 g/cc. Thelow-density filler material may have an average diameter from about 1 toabout 200 μm; from about 5 to about 150 μm; or from about 10 to 100 μm.Exemplary low-density filler materials include silicamicroballoons/microspheres, carbon microballoons, phenolicmicroballoons, or alumina microballoons.

The properties of the microballoons/microspheres that may contribute tothe performance of the ablator composition 110 further comprise densityand wall thickness. More specifically, the wall thickness of themicroballoons according to some implementations of the presentdisclosure is between approximately 1.5 and 2.6 μm. Additionally, thebulk density of the microballoons in some implementations is betweenapproximately 0.15 g/cc (9.5 lb/ft³) and 0.31 g/cc (19.35 lb/ft³).

In some implementations, the low-density filler material comprises fromabout 25% to about 67% by weight of the ablator composition 110. In someimplementations, the low-density filler material comprises from about25% to about 45% by weight of the ablator composition 110. In someimplementations, the low-density filler material comprises from about30% to about 40% by weight of the ablator composition 110.

The endothermically decomposing material functions to remove heat fromthe system as it decomposes. Exemplary endothermically decomposingmaterials include boron-containing compounds, phosphate salts andcombinations thereof. The boron-containing compound may be selected fromthe group consisting of: boric acid and/or salts thereof (sodium borate,sodium tetraborate, or disodium tetraborate), ammonium biborate, andcombinations thereof. Exemplary phosphate salts include ammoniumphosphate (e.g., diammonium hydrogen phosphate.)

Boric acid may be used in implementations where the ablator composition110 cures at an elevated temperature (e.g., approximately 200 degreesFahrenheit or greater (93 degrees Celsius)). Ammonium biborate may beused in implementations where the ablator composition cures at a roomtemperature (e.g., approximately 68 degrees Fahrenheit (20 degreesCelsius)).

In some implementations where boric acid and/or salts thereof arepresent, boric acid and/or salts thereof may comprise greater than 0 andup to about 10% by weight of the ablator composition 110. In someimplementations where boric acid and/or salts thereof are present, boricacid and/or salts thereof may comprise from about 0.1% to about 10% byweight of the ablator composition 110. In some implementations whereboric acid and/or salts thereof are present, boric acid and/or saltsthereof comprise from about 1% to about 10% by weight of the ablatorcomposition 110. In some implementations where boric acid and/or saltsthereof are present, boric acid and/or salts thereof comprise from about2% to about 8% by weight of the ablator composition 110. In someimplementations where boric acid and/or salts thereof are present, boricacid and/or salts thereof comprise from about 3% to about 5% by weightof the ablator composition 110.

In some implementations where ammonium biborate is present, ammoniumbiborate may comprise greater than 0 and up to about 10% by weight ofthe ablator composition 110. In some implementations where ammoniumbiborate is present, ammonium biborate may comprise from about 0.1% toabout 10% by weight of the ablator composition 110. In someimplementations, ammonium biborate may comprise from about 1% to about10% of the ablator composition 110. In some implementations whereammonium biborate is present, ammonium biborate may comprise from about2% to about 8% by weight of the ablator composition 110. In someimplementations where ammonium biborate is present, ammonium biboratemay comprise from about 3% to about 5% by weight of the ablatorcomposition 110.

In some implementations where ammonium phosphate dibasic is present,ammonium phosphate may comprise 10% or less of the ablator composition110. In some implementations, ammonium phosphate may comprise from about0.1% to about 10% of the ablator composition 110. In someimplementations, ammonium phosphate may comprise from about 1% to about10% of the ablator composition 110. In some implementations whereammonium phosphate is present, ammonium phosphate may comprise fromabout 2% to about 8% by weight of the ablator composition 110. In someimplementations where ammonium phosphate is present, ammonium phosphatemay comprise from about 3% to about 5% by weight of the ablatorcomposition 110.

Optionally a thinning fluid/solvent is added to adjust the viscosity ofthe base silicone resin according to the forming method being used. Theamount and type of thinning fluid used is typically dependent on theforming method used. In some implementations, the thinning fluid alsopolymerizes and contributes to the strength and ablation resistance ofthe ablator composition. In some implementations, the thinning fluid mayact as an inhibitor that further extends the pot-life of the ablatorcomposition 110.

For example, for the molded form of the ablator composition, thethinning fluid may be a polydimethylsiloxane (silicone oil) basedthinning fluid such as Dow Corning® 200 fluid, supplied by the DowCorning Corporation. In another example, for the sprayed form of theablator composition 110, one exemplary thinning fluid is a volatilemethylsiloxane (VMS) thinning fluid such as Dow Corning® OS-10 fluidcommercially available from the Dow Corning Corporation. Other exemplarythinning fluids include SYLGARD® 527 A&B Silicone Dielectric Gel orSYLGARD® 537 One Part Dielectric Gel available from the Dow CorningCorporation. SYLGARD® 537 may be used in ablator formulations where itis desirable to cure the ablator formulation at elevated temperatures.SYLGARD® 527 may be used in ablator formulations where it is desirableto cure the ablator formulation at room temperature. Other thinningfluids that provide the desired viscosity for the specific applicationof the ablator composition 110 may also be used.

In some implementations, the thinning fluid comprises about 20% or lessof the ablator composition 110. In some implementations where thethinning fluid is present, the thinning fluid may comprise 10% or lessof the ablator composition 110. In some implementations, the thinningfluid may comprise 5% or less of the ablator composition 110. In someimplementations, the thinning fluid comprises from about 0% and up toabout 20% by weight of the ablator composition 110. In someimplementations, the thinning fluid comprises greater than 0% and up toabout 20% by weight of the ablator composition 110. In someimplementations, the thinning fluid comprises from about 0.1% to about20% by weight of the ablator composition 110. In some implementations,the thinning fluid comprises from about 1% to about 15% by weight of theablator composition 110. In some implementations, the thinning fluid maycomprise from about 1% to about 10% of the ablator composition 110. Insome implementations, the thinning fluid may comprise from about 1% toabout 5% by weight of the ablator composition 110. In someimplementations, the thinning fluid may comprise from about 2% to about4% by weight of the ablator composition 110.

In some implementations, the ablator composition of the presentdisclosure may further comprise additional additives. The additionaladditives may comprise filler materials. Exemplary additional fillermaterials include fiber filler materials and/or powder filler materials.The filler may comprise, for example, an oxide ceramic such as silica(SiO₂), alumina (Al₂O₃), mullite (Al₂O₃—SiO₂), titanium dioxide (TiO₂),or silicon carbide (SiC), wherein the fillers provide additionalmechanical properties to the ablator composition. Other fiber fillerssuch as carbon may also be used; however, the RF transparency of thematerial will be adversely affected.

In some implementations where titanium dioxide (TiO₂) is present,titanium dioxide may comprise 10% or less of the ablator composition110. In some implementations, titanium dioxide may from about 0% toabout 10% of the ablator composition 110. In some implementations,titanium dioxide may comprise from about 2% to about 8% by weight of theablator composition 110. In some implementations, titanium dioxide maycomprise from about 5% to about 7% by weight of the ablator composition110.

In some implementations where silicon carbide is present, siliconcarbide may comprise 10% or less of the ablator composition 110. In someimplementations, silicon carbide may comprise 5% or less of the ablatorcomposition 110. In some implementations, silicon carbide may comprisefrom about 0% to about 10% of the ablator composition 110. In someimplementations, silicon carbide may comprise from about 2% to about 8%by weight of the ablator composition 110. In some implementations,silicon carbide may comprise from about 5% to about 7% by weight of theablator composition 110.

The ablator composition of the present disclosure may be fabricated ormixed for application by first mixing the liquid resin components. Theprescribed percent by weight of base silicone resin is added to acontainer. Next, in implementations where a thinning fluid is used, theprescribed percent by weight of thinning fluid is added. Then theprescribed percent by weight of curing agent/catalyst is added. Thecombination of the base silicone resin, the optional thinning fluid, andthe cuing agent are then thoroughly mixed to ensure that the componentsare uniformly dispersed.

Next, heavier solids such as the boron containing components (e.g.,boric acid, ammonium biborate), ammonium phosphate and silicon carbide(if present) are added and mixed. Prior to addition, the boric acid maybe sieved to achieve a certain particle size. The boron-containingcompound may be added slowly to avoid clumping. Next, ammonium phosphatedibasic crystals are added to the mixture. Additional solids (e.g.,silicon carbide, titanium dioxide, etc.) may be added at this time also.The mixture, including the solids, is then thoroughly mixed to ensurethat the components are uniformly dispersed.

After addition of the heavier solids, the microballoons are added andmixed with the resin. Initially, the mixture, including themicroballoons may be mixed in short pulses to wet the microballoonsfollowed by continuous mixing until a uniform resin/filler blend isattained. The mixing time may be minimized to reduce the possibilitythat the microballoons will crush. Accordingly, a variety ofmanufacturing techniques can be used to fabricate the final ablativestructure.

Exemplary forming methods of the ablator composition 110 comprise manualapplication to a surface, open and closed die molding, spraying,troweling, vacuum forming, extrusion and manual application, althoughother methods commonly known in the art may also be used. The ablatorcomposition 110 may be formed into a geometrical shape using any of theaforementioned methods. The ablator composition 110 may either beco-bonded with the structure that is to be protected or secondarilybonded thereon. With spraying, the bond between the ablator composition110 and the structure is typically created simultaneously with thespraying operation and secondary bonding is generally not required.However, a coupling agent may be applied to the structure to furtherstrengthen the bond of the ablator composition 110 with the structurewhen using spraying methods. Alternately, the coupling agent may be usedto strengthen the bond of the ablator composition 110 with the structurewith other forming methods such as a molded composition that isco-bonded. Exemplary spraying methods further comprise, but are notlimited to, single nozzle, multiple nozzle, convergent spraying, andother spraying methods commonly known in the art. Moreover, the ablatorcomposition 110 may be mixed within the spray system rather than beingpre-mixed prior to application. The ablative structure may bepost-formed to control the thickness and surface finish.

After forming, the ablator composition 110 is preferably subjected to aheat cure. In some implementations where the ablator composition 110cures at an elevated temperature of at least approximately 65.6 degreesCelsius (150 degrees Fahrenheit) and no more than approximately 149degrees Celsius (300 degrees Fahrenheit) for approximately one (1) hourto four hours. In some implementations, where the ablator composition110 cures at an elevated temperature of approximately 93 degrees Celsius(200 degrees Fahrenheit) for approximately 3.5 hours. However, thespecific cure cycle will depend on the geometry of the part, thespecific composition, and the associated tooling, among others. Forexample, a typical cure cycle for a 14″×24″×1″ flat molded panel of theablator composition is approximately 121 degrees Celsius (250 degreesFahrenheit) for approximately two (2) hours. Additionally, the ablatorcomposition will cure at room temperature, however, the cure time rangesbetween approximately four (4) to ten (10) days and may be prohibitivein a high production environment. Other heating methods commonly knownin the art, including but not limited to, microwave, autoclave, andothers may also be used to cure the ablator composition 110 according tothe present disclosure. In addition, the ablative structure may furtherbe post formed and subjected to a further cure cycle to control thethickness and the surface finish thereof.

Depending on the forming method, the viscosity of the ablatorcomposition 110 may be varied to provide for sufficient wetting of themicroballoons and ease of fabrication. With manual application, ortroweling, the dynamic viscosity of the ablator composition 110 in oneform is approximately between 10⁴ Pa-s and 10⁵ Pa-s. For instance, thetrowelable mixture does not flow under its own weight at roomtemperature and has a paste or grout-like consistency. Additionally, theviscosity for spraying is somewhat lower than that of the trowelablemixture yet somewhat higher than that of the raw materials.

Referring to FIG. 3, the ablator composition described above can bereinforced to provide additional structural properties by integrating ahoneycomb core 300 within its composition. In one exemplary method, alayer of the ablator composition 110 is placed throughout a cavity of amold and a piece of honeycomb core 300 is placed over and subsequentlypressed into the ablator composition 110. Alternately, a layer of theablator composition 110 is placed in the cavity of the mold, followed bythe honeycomb core 300, and then followed by another layer of theablator composition 110.

In another exemplary method, the honeycomb core 300 is bonded to astructure first with a film adhesive. The bond is physically andvisually verified, and then the ablator composition 110 is packed intothe open face of the honeycomb core 300 and cured.

With the honeycomb core implementation of the present disclosure, theforming method may be closed-die molding where the material is eithervacuum bagged or placed into a hot press to ensure the honeycomb core300 is uniformly filled with the ablator composition 110. In one form,the material is preferably cured at approximately 149 degrees Celsius(300 degrees Fahrenheit) for approximately one hour. The honeycomb core300 may be a phenolic fiberglass material; however, other honeycomb corematerials commonly known in the art may also be incorporated with theablator compositions 110 according to the properties that are desired.

In addition to the honeycomb core 300, alternate reinforcedimplementations comprise a two-dimensional woven material or a non-wovenmaterial as the reinforcement member. Accordingly, the reinforcement maycomprise continuous or discontinuous fiber forms commonly known in theart. Similar to the honeycomb implementations, the two-dimensional wovenand non-woven reinforced structures comprise the reinforcementimpregnated with the ablator composition 110. The resulting structuremay be formed using a variety of manufacturing techniques, such as themanual troweling method previously described in connection with thehoneycomb core reinforcement implementations. Benefits of reinforcementwith the honeycomb core 300 and the alternate reinforced implementationsinclude char retention and crack suppression.

Referring to FIG. 4, the surface of an ablative structure describedabove can further be “scored” to suppress surface cracking during andafter heat exposure. The scoring 450 may comprise a regular pattern ofsurface indentation, approximately 0.254 cm (0.10 in.) in depth and at aspacing of approximately 2.54 cm (1 inch), which is created prior to orafter curing the ablative structure. As will be appreciated by thoseskilled in the art, the depth and spacing of scoring 450 may varyaccording to specific materials and performance requirements. Moreover,alternate patterns other than the square grid scoring as illustrated mayalso be employed.

EXAMPLES

Aspects and advantages of the embodiments described herein are furtherillustrated by the following examples. The particular materials andamounts thereof, as well as other conditions and details, recited inthese examples should not be used to limit the embodiments describedherein. Examples of the present disclosure are identified by the letter“E” followed by the sample number while comparative samples, which arenot examples of the present disclosure are designated by the letter “C”followed by the sample number. All parts and percentages are by weightunless otherwise indicated.

A description of the raw materials used in the examples is as follows:

Ammonium biborate Available from SIGMA-ALDRICH ® as ammonium biboratetetrahydrate ((NH₄)₂B₄O₇•4H₂O). Boric Acid Available fromSIGMA-ALDRICH ®. ammonium phosphate dibasic Available fromSIGMA-ALDRICH ®. Eccospheres ® SI-200 Hollow thin-walled glassmicroballoons composed mainly of silica (>95% SiO₂) and having aparticle diameter ranging from 5 to 150 microns, commercially availablefrom Trelleborg AEM. SYLGARD ® 182 Silicone A one-part siliconeelastomer commercially available from the Dow Corning Corp. SYLGARD ®184 Silicone A two-part silicone elastomer kit that includes both thesilicone resin and the curing agent and is commercially available fromthe Dow Corning Corp. SYLGARD ® 527 A&B Silicone A two-part siliconeelastomer kit that includes both the silicone resin and the curing agentand is commercially available from the Dow Corning Corp.SYLGARD® 537 One Part Dielectric Gel A one-part, clear, heat cure, lowviscosity gel.

Exemplary formulations used for producing the ablator composition aregiven in Table I. Comparative Example #1 (C1) is a formulation for a lowdensity, room temperature curing ablator formulation. ComparativeExample #2 (C2) is a formulation for a high density, room temperaturecuring ablator formulation. Example #1 (E1) is a formulation for a lowdensity, long out-time ablator formulation. Example #2 (E2) is aformulation for a medium density, long out-time ablator formulation.Example #3 (E3) is a formulation for a high density, long out-timeablator formulation. Example #4 (E4) is a formulation for a mediumdensity, room temperature curing ablator formulation. Example #5 (E5) isa formulation for a low density, long out-time ablator formulationincluding ammonium biborate. Example #6 (E6) is a formulation for amedium density, long out-time ablator formulation including ammoniumbiborate.

TABLE I Table I. Formulations: Component C1 C2 E1 E2 E3 E4 E5 E6Ammonium Biborate 3.42 4.02 Boric Acid 3.42 4.02 4.55 4.02 3.42 4.02Ammonium Phosphate Dibasic 3.42 4.02 4.55 4.02 Eccospheres ® SI-200 46.027.6 43.7 33.8 25.0 33.8 43.7 33.8 Silicon Carbide Powder SYLGARD ® 182Base 42.5 49.7 56.3 42.5 49.7 SYLGARD ® 182 Curing Agent 4.25 4.97 5.634.25 4.97 SYLGARD ® 184 Base 36.2 46.9 49.7 SYLGARD ® 184 Curing Agent3.62 4.69 4.97 SYLGARD ® 527 part A 7.1 10.45 1.7 SYLGARD ® 527 part B7.1 10.45 1.7 SYLGARD 537 2.8 3.5 3.9 2.8 3.5 Total 100 100 100 100 100100 100 100

Test Methods:

Thermal performance of the disclosed ablator formulation wasdemonstrated by exposure to heating in the NASA Johnson Space CenterAtmospheric Reentry Materials and Structures Evaluation Facility(ARMSEF) ‘arc jet facility’ at conditions representative of atmosphericentry from low earth orbit. The test coupons were axisymmetric with a 4inch (10.16 cm) diameter and a 2 inch (5.08 cm) height. The 4 inchradius curvature of the forward face creates an Iso-Q surface meaningthat under arcjet heating conditions, the forward surface of the modelshould experience nearly uniform heat flux. Two test couponconfigurations were used. The first test configuration had aninstrumented thermocouple plug for measuring in-depth temperatureresponse and a second test coupon configuration with just a bondlinethermocouple, positioned at the interface between the ablative materialand the substrate (e.g., aluminum or composite material bonded to thebackside)

The various test formulations of the ablator composition were exposed tonominal and max heat rate entry heating conditions representative of lowEarth orbit entry for a manned capsule.

Results:

Test coupons including the disclosed ablator formulation exhibitedsignificantly reduced backface temperature and swelling/splitting undernominal entry heating conditions relative to test coupons includingknown compositions.

In some implementations, the density of the ablator compositiondescribed herein is approximately 0.3 to 0.6 g/cc (approximately 18.7 to37.5 lb/ft³), which is relatively low compared to ablator compositionsof the known art. In addition, the ablator composition described hereinhas high erosion resistance and durability. The ablator compositiondescribed herein has been tested under high Mach conditions and haswithstood temperatures up to approximately 1650 degrees Celsius (3002degrees Fahrenheit) with near zero recession in low Earth orbit entryheating environments. In addition, the room temperature thermalconductivity of the ablator composition is relatively low atapproximately 0.13 W/m-K.

Further preliminary testing has shown that the ablator compositiondescribed herein has a tensile strength greater than approximately 689kPa (100 lb/in²) (e.g., from about 689 kPa (100 lb/in²) up to about 2068kPa (300 lb/in²)). Variations on properties of the ablator compositiondescribed herein may vary according to the constituent elementscontained therein, and therefore, the properties disclosed herein aremerely exemplary and shall not be construed as limiting the scope of thepresent disclosure.

In preliminary high flow rate testing against commercially availableablative materials, the ablator composition described hereinconsistently delivered low backface temperatures, low char density, andexcellent char durability. Accordingly, the ablator compositiondescribed herein has improved thermal properties, erosion resistance,and durability over various other ablator compositions of the known art,while providing low-density and low cost thermal protection.

Inclusion of boric acid in the ablator composition may allow the silicaglass microballoon filler to fuse in the decomposition zone creating anetwork of glass reinforcement in the weaker decomposition zone withoutthe effects of glass fiber reinforcement increasing the weight ordensity. It has been found that using boric acid provides multipleadvantages including cooling and providing a boron source.

While the foregoing is directed to embodiments of the presentdisclosure, other and further embodiments of the present disclosure maybe devised without departing from the basic scope thereof, and the scopethereof is determined by the claims that follow.

1-20. (canceled)
 21. A reinforced ablator structure, comprising: anablator composition, comprising: about 30 to about 70 percent by weightof a base silicone resin; about 25 to about 67 percent by weight of alow-density filler; about 3 to about 7 percent by weight of a curingagent; greater than 0 and up to about 10 percent by weight of aboron-containing compound; and greater than 0 and up to about 10 percentby weight of ammonium phosphate dibasic; and a honeycomb core integratedwith the ablator composition.
 22. The reinforced ablator structure ofclaim 21, wherein the boron-containing compound is selected from boricacid and salts thereof, ammonium biborate, or a combination thereof. 23.The reinforced ablator structure of claim 22, wherein theboron-containing compound is boric acid and salts thereof and is presentfrom about 3 to about 5 percent by weight.
 24. The reinforced ablatorstructure of claim 21, wherein the ammonium phosphate dibasic is presentfrom about 3 to about 5 percent by weight.
 25. The reinforced ablatorstructure of claim 21, wherein the ablator composition further comprisesgreater than 0 and up to about 20 percent by weight of a thinning fluid.26. The reinforced ablator structure of claim 21, wherein thelow-density filler comprises silica microballoons.
 27. The reinforcedablator structure of claim 21, wherein the density of an ablatormaterial formed by curing the ablator composition ranges between atleast 0.3 and about 0.6 g/cc.
 28. The reinforced ablator structure ofclaim 21, wherein the ablator composition is uncured.
 29. The reinforcedablator structure of claim 21, wherein the honeycomb core comprises aphenolic resin material.
 30. A vehicle comprising the reinforced ablatorstructure of claim
 21. 31. The vehicle of claim 30, wherein the vehiclecomprises manned and unmanned space vehicles, mobile airborne vehicles,ground based vehicles, or marine vehicles.
 32. A method of making areinforced ablator structure, comprising: integrating a honeycomb corewith an ablator composition, wherein the ablator composition comprises:about 30 to about 70 percent by weight of a base silicone resin; about25 to about 67 percent by weight of a low-density filler; about 3 toabout 7 percent by weight of a curing agent; greater than 0 and up toabout 10 percent by weight of a boron-containing compound; and greaterthan 0 and up to about 10 percent by weight of ammonium phosphatedibasic.
 33. The method of claim 32, wherein integrating the honeycombcore with the ablator composition comprises: depositing a layer of theablator composition in a cavity of a mold; and pressing a piece of thehoneycomb core into the ablator composition.
 34. The method of claim 32,wherein integrating the honeycomb core with the ablator compositioncomprises: bonding the honeycomb core to a structure; packing theablator composition into an open face of the honeycomb core; and curingthe honeycomb core and the ablator composition.
 35. The method of claim34, further comprising scoring the honeycomb core prior to curing thehoneycomb core and the ablator composition.
 36. The method of claim 32,wherein integrating the honeycomb core with the ablator compositioncomprises a closed-die molding process.
 37. The method of claim 32,further comprising adjusting the viscosity of the ablator composition byadding greater than 0 and up to about 20 percent by weight of a thinningfluid to the ablator composition.
 38. The method of claim 32, whereinthe boron-containing compound is selected from boric acid and saltsthereof, ammonium biborate, or a combination thereof.
 39. The reinforcedablator structure of claim 32, wherein the boron-containing compound isboric acid and salts thereof and is present from about 3 to about 5percent by weight.
 40. The reinforced ablator structure of claim 32,wherein the ammonium phosphate dibasic is present from about 3 to about5 percent by weight.